Redox flow battery

ABSTRACT

A redox flow (RF) battery is provided that performs charge and discharge by supplying a positive electrode electrolyte and a negative electrode electrolyte to a positive electrode cell and a negative cell, respectively. Each of the positive and negative electrode electrolytes contains a vanadium (V) ion as active material. At least one of the positive and negative electrode electrolytes further contains another metal ion, for example, a manganese ion that exhibits a higher redox potential than a V ion or a chromium ion that exhibits a lower redox potential than a V ion. Even in cases where the RF battery is nearly fully charged, side reactions such as generation of oxygen has or hydrogen gas due to water decomposition and oxidation degradation of an electrode can be suppressed since the above-mentioned another metal ion contained together with the V ion is oxidized or reduced in the late stage of charge.

TECHNICAL FIELD

The present invention relates to a redox flow battery containing avanadium ion as active material, and particularly to a redox flowbattery capable of improving an energy density as compared to theconventional vanadium redox flow battery.

BACKGROUND ART

As a way to combat global warming, introduction of new energy such assolar photovoltaic power generation and wind power generation has beenpromoted in recent years throughout the world. Since outputs of suchpower generation are affected by the weather, it is predicted thatintroduction on a large scale will cause problems with operation ofpower systems such as difficulty in maintaining frequencies andvoltages. As a way to solve such problems, installation oflarge-capacity storage batteries for smoothing output variations,storing surplus power, and load leveling is expected.

A redox flow battery is one of large-capacity storage batteries. In aredox flow battery, a positive electrode electrolyte and a negativeelectrode electrolyte are supplied to a battery cell having a membraneinterposed between a positive electrode and a negative electrode, tocharge and discharge the battery. An aqueous solution containing awater-soluble metal ion having a valence which changes byoxidation-reduction is representatively used as the electrolytes, andsuch a metal ion is used as active material. In recent years, the mostwidely studied type is a vanadium redox flow battery in which a vanadium(V) ion is used as active material for each of the positive electrodeand the negative electrode (for example, Patent Literatures 1 and 2).The vanadium redox flow battery is currently put in practical use andexpected to be continuously used in the future.

CITATION LIST Patent Literature PTL 1: Japanese Patent No. 3143568 PTL2: Japanese Patent Laying-Open No. 2003-157884 SUMMARY OF INVENTIONTechnical Problem

However, it is difficult for the conventional vanadium redox flowbattery to achieve a further improvement in the energy density.

Generally, batteries are desired to have a higher energy density. Inorder to increase the energy density, for example, it is conceivable toraise the solubility of the active material in the electrolyte and toraise the utilization rate of the electrolyte, that is, the utilizationrate of the metal ion contained as active material in the electrolyte.The above-described utilization rate means the actually availablebattery capacity (discharge capacity) with respect to the theoreticalbattery capacity (Ah) of the above-mentioned metal ion, that is, thedifference between the battery capacity in the lower limit state ofcharge (SOC) and the battery capacity in the upper limit state ofcharge.

However, when the above-described utilization rate is raised as much aspossible for charging, in other words, when the state of charge isincreased, in the late stage of charge, the positive electrode undergoesa side reaction such as generation of oxygen resulting from waterdecomposition and deterioration of electrodes (particularly, made ofcarbon materials) while the negative electrode undergoes a side reactionsuch as generation of hydrogen resulting from water decomposition sincean aqueous solution is utilized for an electrolyte as described above inthe typical configuration of the redox flow battery.

The above-described side reactions bring about a lot of harmful effectssuch as (1) a current loss (a loss caused by the fact that a part of thequantity of electricity (Ah) used during charge is not used for abattery reaction (valence change) but is used for another reaction suchas decomposition of water and the like) is caused to decrease thebattery efficiency; (2) a difference between the states of charge of thepositive and negative electrodes is caused, leading to a reduction inthe available battery capacity; (3) deterioration of electrodes causes ashortened battery lifetime; and the like. Accordingly, when the batteryis actually operated, the voltage at which charge is stopped (upperlimit charge voltage) is determined so as to use the battery to such adegree that the above-described side reaction does not occur. Forexample, in order to suppress the above-described side reactions, PatentLiterature 1 proposes that a pentavalent V ion in the positive activematerial is 90% or less at the end of charge while Patent Literature 2proposes that charge is to be continued such that a divalent V ion inthe negative active material is 94% or less.

However, the cell resistance is increased in the long-term use.Accordingly, when the voltage at which charge is to be stopped is set ata constant value without being changed from the beginning of its use,the cell resistance is increased, so that the state of charge at thestart of its use cannot be maintained. Therefore, the voltage at whichcharge is stopped is to be increased over time in order to ensure aprescribed state of charge. Consequently, it becomes difficult to ensurea high state of charge without generating oxygen gas and hydrogen gasfor a long period of time.

From the viewpoint of suppression of a side reaction, it is difficult inthe current situation to keep the state of charge of a vanadium ion inthe electrolyte at 90% or higher for a long period of time, andtherefore, the vanadium ion cannot be sufficiently utilized. For thatreason, in the conventional vanadium redox flow battery, it is difficultto achieve the utilization rate of the vanadium ion at 90% or higher,and still higher. Thus, an improvement in the energy density is limited.

An object of the present invention is to provide a redox flow batterythat can improve an energy density.

Solution to Problem

In the conventional vanadium redox flow battery, only a vanadium ion isused as a metal ion serving as active material. On the other hand, thepresent inventors have surprisingly found that the utilization rate of avanadium ion can be greatly improved as compared to the conventionalvanadium redox flow battery, for example, by causing the electrolytecontaining a vanadium ion as active material to contain metal ions suchas a manganese (Mn) ion that is higher in oxidation-reduction potential(hereinafter simply referred to as potential) than the vanadium ion onthe positive electrode side and a metal ion such as a chromium (Cr) ionthat exhibits a lower redox potential than the vanadium ion on thenegative electrode side, together with the vanadium ion. This isconsidered to result from the reasons described below.

In the redox flow battery using the electrolyte containing a vanadiumion as active material, the following reaction occurs in each electrodeupon charging. The standard potentials at the time of occurrence of thereaction in each electrode are also shown.

Charge (positive electrode): V⁴⁺→V⁵⁺+e⁻ Potential: about 1.0V (V⁴⁺/V⁵⁺)

Charge (negative electrode): V³⁺+e⁻→V²⁺Potential: about −0.26V (V³⁺/V²⁺)

Furthermore, the following side reaction may occur in the late stage ofcharge. Also shown in this case is the standard potential at the time ofoccurrence of each reaction when the electrode made of carbon materialis utilized.

Charge (positive electrode):

H₂O→(½)O₂+2H⁺+2e ⁻

-   -   Potential: about 1.2V (actual potential: about 2.0V)

C (carbon)+O₂→CO₂+4e ⁻

-   -   Potential: about 1.2V (actual potential: about 2.0V)

Charge (negative electrode):

H⁺ +e ⁻→(½)H₂

-   -   Potential: about 0V (actual potential: about −0.5V)

In the actual operation, an overvoltage depending on the used electrodematerial is required, in which case the potential at the time ofoccurrence of the actual side reaction on the positive electrode sidetends to be higher than the standard value. For example, when theelectrode material is carbon material, the potential at the time ofcarbon reaction or water decomposition is about 2V, which is higher thanabout 1V that is the potential at the time of occurrence of batteryreaction in the positive electrode. Therefore, an oxidation reaction ofa vanadium ion (V⁴⁺→V⁵⁺) mainly occurs in the positive electrode duringcharge as described above. However, when the charge voltages rises inthe late stage of charge to cause the potential of the positiveelectrode to be relatively high, generation of oxygen gas and oxidationdegradation of electrodes (carbon) may occur together with theabove-described oxidation reaction of the vanadium ion. Furthermore,this side reaction also leads to deterioration of the batterycharacteristics.

Furthermore, in the actual operation, the potential at the time ofoccurrence of the actual side reaction on the negative electrode sidetends to be lower than the standard value, depending on the usedelectrode material. For example, in the case where the electrodematerial is carbon material, a hydrogen overvoltage is relatively large,with the result that the potential at the time of generation of hydrogenis approximately −0.5V, which further exhibits a lower redox potentialthan approximately −0.26V that is the potential at the time ofoccurrence of the battery reaction in the negative electrode. Therefore,during charge, a reduction reaction of the vanadium ion (V³⁺→V²⁺) mainlyoccurs as described above in the negative electrode. However, when thecharge voltage rises in the late stage of charge to cause the potentialof the negative electrode to be relatively low, hydrogen gas may begenerated simultaneously with the above-described reduction reaction ofthe vanadium ion.

In contrast, the following is the case where the positive electrodeelectrolyte contains, in addition to a vanadium ion, a metal ion higherin redox potential than a vanadium ion. For example, the potential ofMn²⁺/Mn³⁺ is approximately 1.5V, which is higher than the potential ofV⁴⁺/V⁵⁺(approximately 1.0V). In this case, however, this potentialexists on the lower side with respect to the actual potential(approximately 2V) at the time of occurrence of a side reaction on thepositive electrode side such as generation of oxygen gas resulting fromwater decomposition or electrode oxidation as described above.Accordingly, for example, when a divalent manganese ion (Mn²⁺) iscontained, an oxidation reaction of Mn²⁺ is to first occur beforeoccurrence of the side reaction on the positive electrode side such asgeneration of oxygen gas described above. In other words, in the latestage of charge, together with the oxidation reaction of V⁴⁺ that is amain reaction of the battery, an oxidation reaction of Mn²⁺ also occursas a part of the battery reaction. The oxidation reaction of the metalion different from the vanadium ion occurs, so that the above-describedside reaction on the positive electrode side can be suppressed.

Alternatively, the following is the case where the negative electrodeelectrolyte contains, in addition to a vanadium ion, a metal ion lowerin redox potential than the vanadium ion. For example, the potential ofCr³⁺/Cr²⁺ is approximately −0.42V that is lower than the potential ofV³⁺/V²⁺ (approximately −0.26V). In this case, however, this potentialexists on the higher side with respect to the actual potential(approximately −0.5V) at the time of occurrence of the side reaction onthe negative electrode side such as generation of hydrogen gas describedabove. Accordingly, for example, in the case where a trivalent chromiumion (Cr³⁺) is contained, a reduction reaction of Cr³⁺ is to first occurbefore occurrence of the above-described side reaction on the negativeelectrode side. In other words, in the late stage of charge, togetherwith the reduction reaction of V³⁺ that is a main reaction of thebattery, reduction reaction of Cr³⁺ also occurs as part of the batteryreaction. The reduction reaction of the metal ion different from thevanadium ion occurs, so that the above-described side reaction on thenegative electrode side can be suppressed.

As described above, in the case where the positive electrode electrolytecontains not only a vanadium ion but also a metal ion higher in redoxpotential than the vanadium ion, and in the case where the negativeelectrode electrolyte contains not only a vanadium ion but also a metalion lower in redox potential than the vanadium ion, the above-describedside reaction hardly occurs or substantially does not occur, forexample, even when charge is performed such that the state of charge ofthe electrolyte in each of the positive electrode and the negativeelectrode exceeds 90%. Therefore, in the embodiment where theabove-described metal ion is contained, it is considered that thevanadium ion in the electrolyte can be fully utilized repeatedly withstability as compared to the conventional vanadium redox flow battery.Thus, the utilization rate of the vanadium ion is enhanced in this way,thereby allowing improvement in the energy density. The presentinvention is based on the above-described findings.

The present invention relates to a redox flow battery performing chargeand discharge by supplying a positive electrode electrolyte and anegative electrode electrolyte to a battery cell. Each of the positiveelectrode electrolyte and the negative electrode electrolyte contains avanadium ion. Furthermore, at least one of the positive electrodeelectrolyte and the negative electrode electrolyte further contains atleast one of a metal ion higher in redox potential than a vanadium ionand a metal ion lower in redox potential than the vanadium ion.

The redox flow battery according to the present invention having theabove-described configuration allows suppression of the side reaction inthe late stage of charge even when charge is performed until the stateof charge of the electrolyte in at least one of the positive electrodeand the negative electrode reaches nearly 100%. Specifically, forexample, on the positive electrode side, oxidation of another metal ion(specifically, a metal ion higher in redox potential than a vanadium ionon the positive electrode side) contained together with a vanadium ionallows suppression of the side reaction such as generation of oxygen gasresulting from water decomposition and oxidation degradation of theelectrode as described above. For example, on the negative electrodeside, reduction of another metal ion (specifically, a metal ion lower inredox potential than a vanadium ion on the negative electrode side)contained together with a vanadium ion allows suppression of the sidereaction such as generation of hydrogen gas as described above.Accordingly, as compared to the conventional redox flow battery that canonly raise the state of charge to at most approximately 90% due to theside reaction occurring in the late stage of charge, the redox flowbattery according to the present invention can raise the state of chargeof the electrolyte in at least one of the electrodes to nearly 100%. Thestate of charge can be raised in this way, thereby allowing an increasein the utilization rate of the vanadium ion in the electrolyte.Accordingly, the redox flow battery according to the present inventioncan improve the energy density as compared to the conventional case.

Furthermore, since the redox flow battery according to the presentinvention can suppress the side reaction as described above, it can alsoeffectively suppress various defects (decreased battery efficiency,decreased battery capacity, shortened lifetime) caused by the sidereaction. Thus, since the redox flow battery according to the presentinvention is not only excellent in battery characteristics but alsocapable of increasing the durability, high reliability can be ensuredfor a long period of time.

Examples of a representative embodiment of the present invention will bedescribed as follows. In each of the following embodiments, a metal ionhigher in redox potential than a vanadium ion exists at least in thepositive electrode electrolyte, and a metal ion lower in redox potentialthan a vanadium ion exists at least in the negative electrodeelectrolyte, so that the side reaction in the late stage of charge canbe effectively suppressed as described above, thereby allowing anincrease in the utilization rate of the vanadium ion.

(1) The embodiment in which at least the positive electrode electrolytecontains a vanadium ion and a metal ion higher in redox potential thanthe vanadium ion while the negative electrode electrolyte contains thevanadium ion.

(2) The embodiment in which each of the positive electrode electrolyteand the negative electrode electrolyte contains a vanadium ion and ametal ion higher in redox potential than the vanadium ion.

(3) The embodiment in which at least the positive electrode electrolytecontains a vanadium ion, a metal ion higher in redox potential than thevanadium ion and a metal ion lower in redox potential than the vanadiumion while the negative electrode electrolyte contains the vanadium ion.

(4) The embodiment in which at least the positive electrode electrolytecontains a vanadium ion, a metal ion higher in redox potential than thevanadium ion and a metal ion lower in redox potential than the vanadiumion while at least the negative electrode electrolyte contains avanadium ion and a metal ion higher in redox potential than the vanadiumion.

(5) The embodiment in which the positive electrode electrolyte containsa vanadium ion while at least the negative electrode electrolytecontains a vanadium ion and a metal ion lower in redox potential thanthe vanadium ion.

(6) The embodiment in which each of the positive electrode electrolyteand the negative electrode electrolyte contains a vanadium ion and ametal ion lower in redox potential than the vanadium ion.

(7) The embodiment in which the positive electrode electrolyte containsa vanadium ion while at least the negative electrode electrolytecontains a vanadium ion, a metal ion higher in redox potential than thevanadium ion and a metal ion lower in redox potential than the vanadiumion.

(8) The embodiment in which at least the positive electrode electrolytecontains a vanadium ion and a metal ion lower in redox potential thanthe vanadium ion while at least the negative electrode electrolytecontains a vanadium ion, a metal ion higher in redox potential than thevanadium ion and a metal ion lower in redox potential than the vanadiumion.

Particularly, it is preferable to provide the embodiment in which atleast the positive electrode electrolyte further contains a metal ionhigher in redox potential than the vanadium ion while at least thenegative electrode electrolyte further contains a metal ion lower inredox potential than the vanadium ion, since the side reaction in thelate stage of charge described above is further effectively suppressed,thereby allowing a further increase in the utilization rate of thevanadium ion. This embodiment can also be configured such that thepositive electrode electrolyte further contains a metal ion lower inredox potential than the vanadium ion or such that the negativeelectrode electrolyte further contains a metal ion higher in redoxpotential than the vanadium ion.

In addition, it becomes possible to provide the embodiment in which theelectrolyte in each of the positive electrode and the negative electrodecontains a vanadium ion, a metal ion higher in redox potential than thevanadium ion and a metal ion lower in redox potential than the vanadiumion, and representatively, the embodiment in which the electrolytes inboth of the electrodes contain the same metal ion species. In theembodiment in which metal ion species in the both positive and negativeelectrode electrolytes are the same or partially the same, specificeffects as described below may be achieved. Specifically, (1) the metalion higher in redox potential in the positive electrode electrolyte andthe metal ion lower in redox potential in the negative electrodeelectrolyte each move to a counter electrode, to cause a relativedecrease in the metal ion essentially reacting on each electrode, sothat it becomes possible to effectively avoid or suppress a decreasedeffect of suppressing the side reaction. (2) Even when liquid transferoccurs over time in accordance with charge/discharge (the phenomenon inwhich the electrolyte in one electrode moves to the other electrode) tocause variations in the amount of the electrolyte in each electrode,mixture of the electrolytes in both of the electrodes allows orfacilitates the variations to be readily corrected. (3)Manufacturability of the electrolyte is excellent. In addition, in theembodiment in which the metal ion species are the same or partially thesame, the metal ion higher in redox potential than the vanadium ionexisting in the negative electrode electrolyte and the metal ion lowerin redox potential than the vanadium ion existing in the positiveelectrode electrolyte exist mainly for the electrolytes in both of theelectrodes to contain partially the same metal ion species, but do notactively act as active materials. Accordingly, the concentration of themetal ion higher in redox potential in the negative electrodeelectrolyte and the concentration of the metal ion higher in redoxpotential in the positive electrode electrolyte may be differently set,and the concentration of the metal ion lower in redox potential in thepositive electrode electrolyte and the concentration of the metal ionlower in redox potential in the negative electrode electrolyte may bedifferently set. However, when these respective concentrations areequally set, the above-described effects (1) to (3) can be readilyachieved.

It is preferable that the above-described metal ion higher in redoxpotential and the above-described metal ion lower in redox potential arewater-soluble similarly to a vanadium ion or soluble in an acid aqueoussolution. It is preferable that the metal ion higher in redox potentialexists on the lower side than the actual potential (approximately 2V) atthe time when a side reaction occurs on the positive electrode side. Itis preferable that the metal ion lower in redox potential exists on thehigher side than the actual potential (approximately −0.5V) at the timewhen a side reaction occurs on the negative electrode side.

Examples of the above-described metal ion higher in redox potential mayinclude at least one type of metal ions, for example, selected from amanganese (Mn) ion, a lead (Pb) ion, a cerium (Ce) ion, and a cobalt(Co) ion. The standard potential of the above-described metal ions isMn²⁺/Mn³⁺: approximately 1.5V, Pb²⁺/Pb⁴⁺: approximately 1.62V,Pb²⁺/PbO₂: approximately 1.69V, Ce³⁺/Ce⁴⁺: approximately 1.7V, andCo²⁺/Co³⁺: approximately 1.82V. Thus, this potential is higher than thepotential of the vanadium ion on the positive electrode side: V⁴⁺/V⁵⁺(approximately 1.0V), and lower than the potential of theabove-described side reaction on the positive electrode side(approximately 2V). In addition to a vanadium ion, the electrolyte ineach of the positive electrode and the negative electrode may containone type of the above-described higher potential metal ion or contain aplurality of types of combined higher potential metal ions havingdifferent potentials.

Examples of the above-described metal ion lower in redox potential mayinclude at least one type of metal ions, for example, of a chromium ionand a zinc ion. The standard potential of chromium is Cr³⁺/Cr²⁺:approximately −0.42V, which is lower than the potential of the vanadiumion on the negative electrode side: V³⁺/V²⁺ (approximately −0.26V) andhigher than the potential of the above-described side reaction on thenegative electrode side (approximately −0.5V). On the other hand, thestandard potential of zinc is Zn²⁺/Zn (metal): approximately −0.76V,which is lower than the potential of V³⁺/V²⁺ (approximately −0.26V) andlower than the potential of the above-described side reaction on thenegative electrode side. However, zinc is sufficiently high in hydrogenovervoltage, and therefore, can cause a battery reaction. In addition toa vanadium ion, the electrolyte in each of the positive electrode andthe negative electrode may contain one type of the above-described lowerpotential metal ion or contain a plurality of types of combined lowerpotential metal ions having different potentials.

As for the above-described metal ions, by utilizing such metal ions asallowing a reversible oxidation-reduction reaction and at leastfunctioning as positive electrode active material or negative electrodeactive material, it becomes possible to decrease the amount of thevanadium ions practically required to store a prescribed electric poweramount (kWh). Therefore, it is expected in this case that metal ionsused as active material can be stabilized and supplied less expensively.The present inventors have found that Mn³⁺ produced by oxidationreaction of Mn²⁺ undergoes a reversible oxidation-reduction reaction inthe sulfuric acid solution, that is, Mn³⁺ oxidized during charge may beused during discharge for the discharge reaction of the battery(Mn³⁺+e⁻→Mn²⁺), and, in addition to a vanadium ion, a manganese ion canbe repeatedly used as active material. Furthermore, among theabove-described metal ions, a manganese ion is excellent in solubility.The above-described chromium ion and zinc ion undergo a reversibleoxidation-reduction reaction in the sulfuric acid solution.Specifically, Cr²⁺ and Zn (metal) reduced during charge are utilizedduring discharge for discharge reaction (Cr²⁺→Cr³⁺+e⁻, Zn→Zn²⁺+2e⁻) ofthe battery and can be repeatedly used as active material. Therefore, itis preferable that the above-described higher potential metal ionscontain a manganese ion while the above-described lower potential metalions contain a chromium ion and a zinc ion.

When the manganese ion is contained as the above-described metal ionhigher in redox potential, there may be a specific embodiment in whichat least one type of a manganese ion of a divalent manganese ion and atrivalent manganese ion is contained. By containing one of theabove-described manganese ion, the divalent manganese ion (Mn²⁺) existsduring discharge and the trivalent manganese ion (Mn³⁺) exists duringcharge, leading to existence of both manganese ions through repeatedcharge and discharge.

In the case of the electrolyte containing the manganese ion as describedabove, it is considered that tetravalent manganese may exist dependingon the state of charge in the actual operation. Therefore, as oneembodiment according to the present invention, an electrolyte containingthe above-described metal ions higher in redox potential contains atleast one type of manganese ions of a divalent manganese ion and atrivalent manganese ion, and tetravalent manganese. In this case, Mn³⁺is unstable, which may cause a disproportionation reaction that producesMn²⁺ (divalent) and MnO₂ (tetravalent) in a manganese ion aqueoussolution. As a result of the study by the present inventors, tetravalentmanganese produced by the disproportionation reaction is considered tobe MnO₂, but this MnO₂ is considered to be not entirely a solidprecipitation but to exist in a stable state in which the MnO₂ seems tobe at least partially dissolved in the electrolyte. This MnO₂ floatingin the electrolyte can be used repeatedly by being reduced to Mn²⁺(discharged) through two-electron reaction during discharge, namely, byserving as active material, to contribute to increase in batterycapacity. Accordingly, the present invention allows existence oftetravalent manganese. In addition, when it is desired to suppressprecipitation of MnO₂ by the disproportionation reaction, for example,it is proposed that the operation is performed such that the state ofcharge of positive electrode manganese is not more than 90%, andpreferably, equal to 70%, and the acid concentration (for example, thesulfuric acid concentration) of the electrolyte is increased when thesolvent of the electrolyte is an acid aqueous solution.

In the case where a chromium ion is contained as the above-describedmetal ion lower in redox potential, as a more specific embodiment, atleast one type of chromium ions of a divalent chromium ion and atrivalent chromium ion may be contained. By containing any one of thechromium ions described above, a trivalent chromium ion (Cr³⁺) existsduring discharge while a divalent chromium ion (Cr²⁺) exists duringcharge, leading to existence of both chromium ions through repeatedcharge and discharge. Chromium is easily treated since it exists alwaysas an ion in an aqueous solution with stability.

The present invention may include an embodiment where at least one ofthe total concentration of the metal ion higher in redox potential inthe electrolyte containing the above-described metal ions higher inredox potential and the total concentration of the metal ion lower inredox potential in the electrolyte containing the above-described metalions lower in redox potential is not less than 0.1M and not more than 5M(M is a mol concentration). More specifically, the present invention mayinclude an embodiment where the total concentration of the metal ionshigher in redox potential is not less than 0.1M and not more than 5Mwhen the positive electrode electrolyte contains the metal ion higher inredox potential; an embodiment where the total concentration of themetal ions lower in redox potential is not less than 0.1M and not morethan 5M when the negative electrode electrolyte contains the metal ionslower in redox potential; and an embodiment where the totalconcentration of the metal ions higher in redox potential and the totalconcentration of the metal ions lower in redox potential each are notless than 0.1M and not more than 5M when the positive electrodeelectrolyte contains the metal ions higher in redox potential and thenegative electrode electrolyte contains the metal ions lower in redoxpotential.

When the total concentration of each of the higher potential metal ionsand the lower potential metal ions existing in the electrolyte of eachof the positive electrode and the negative electrode is less than 0.1M,oxidation reaction and reduction reaction of the metal ions hardlyoccur, leading to difficulty in achieving the effect of suppressing theabove-described side reaction by these oxidation reaction and reductionreaction. Consequently, it becomes difficult to sufficiently improve theenergy density. The higher the total concentration of each of theabove-described metal ions is, the greater the above-described effect ofsuppressing the side reaction is achieved and the more the energydensity is improved. In this case, however, the solubility of thevanadium ion tends to decrease due to increased metal ions. When eachtotal concentration of the above-described metal ions is not more than1M, and further, not more than 0.5M, the effects of suppressing theabove-described side reaction and the like can be achieved while thesolubility of vanadium ion can also be sufficiently ensured.Furthermore, when the solvent of the electrolyte is an acid aqueoussolution as described above and contains a manganese ion, the acidconcentration of the electrolyte is increased to some extent, therebyallowing suppression of precipitation of MnO₂. In this case, however,the increased acid concentration may cause a decrease in the solubilityof metal ions. Accordingly, the upper limit of the total concentrationof the metal ions in each of the electrodes is considered to be 5M.

The present invention includes an embodiment where both the positive andnegative electrode electrolytes contain a sulfate anion (SO₄ ²⁻).

As for the solvent of the electrolyte in each of the positive electrodeand the negative electrode, the aqueous solution containing at least onetype of a sulfate anion (SO₄ ²⁻), a phosphate anion (PO₄ ³⁻) and anitrate anion (NO₃ ⁻) can be suitably utilized. These acid aqueoussolutions can be expected to achieve several effects that (1) thestability, the reactivity and the solubility of the vanadium ion and theabove-described metal ions in the electrolyte may be improved; (2) theion conductivity is increased and the internal resistance of the batteryis reduced, and (3) unlike when hydrochloric acid (HCl) is used,chlorine gas is not generated. Particularly, the embodiment where asulfate anion (SO₄ ²⁻) is contained is preferable since the stabilityand the reactivity of the vanadium ion and the above-described metalions can be improved as compared to the case where a phosphate anion anda nitrate anion are contained. For the electrolyte in each of theabove-described electrodes to contain a sulfate anion, for example, asulfate salt containing a vanadium ion and the above-described metalions may be used.

The present invention includes an embodiment where the solvent of eachof the above-described positive and negative electrode electrolytes isan aqueous solution of H₂SO₄. In this case, it is preferable that thesulfuric acid concentration of the electrolyte in each of the positiveelectrode and the negative electrode is not more than 5M.

In addition to use of the sulfate salt as described above, an H₂SO₄aqueous solution (sulfuric acid aqueous solution) is used as a solventof the electrolyte, so that the stability and the reactivity of thevanadium ion and the metal ion can be improved while the internalresistance can also be reduced as described above. However, when thesulfuric acid concentration is too high, existence of the sulfate anionmay lead to a decrease in the solubility of the vanadium ion and themetal ions such as a manganese ion and a chromium ion, and also lead toan increase in the viscosity of the electrolyte. Accordingly, thesulfuric acid concentration is preferably not more than 5M, in whichcase 1M to 4M can be readily available, and 1M to 3M is more preferable.

The present invention includes an embodiment where the operation iscarried out such that at least one of the state of charge of thepositive electrode electrolyte and the state of charge of the negativeelectrode electrolyte exceeds 90%. More specifically, it is preferablethat the redox flow battery according to the present invention isoperated such that the state of charge of the electrolyte of one of thepositive electrode electrolyte and the negative electrode electrolytecontaining at least one of the metal ions higher in redox potential andthe metal ions lower in redox potential exceeds 90%.

In the present invention, in the state where the positive electrodeelectrolyte contains, in addition to a vanadium ion, a metal ion higherin redox potential than the vanadium ion and the state where thenegative electrode electrolyte contains, in addition to a vanadium ion,a metal ion lower in redox potential than the vanadium ion, the sidereaction can be suppressed as described above even when charge isperformed such that the state of charge exceeds 90%. The state of chargeis increased in this way, the utilization rate of the vanadium ion canbe effectively raised. Particularly in the embodiment where the positiveelectrode electrolyte contains the above-described metal ions higher inredox potential and the negative electrode electrolyte contains theabove-described metal ions lower in redox potential, the state of chargeof each electrolyte in the positive electrode and the negative electrodeis increased to exceed 90%. Thus, it is expected that the utilizationrate of the vanadium ion can be more effectively increased.

Advantageous Effects of Invention

The redox flow battery according to the present invention can improvethe energy density.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 illustrates the operating principles of a battery systemincluding a redox flow battery according to the first embodiment.

FIG. 2 illustrates the operating principles of a battery systemincluding a redox flow battery according to the second embodiment.

FIG. 3 illustrates the operating principles of a battery systemincluding a redox flow battery according to the third embodiment.

FIG. 4 shows a graph illustrating the relation between a cycle time(sec) of charge and discharge and a battery voltage (V) in an examplesystem manufactured in Experimental Example 1.

FIG. 5 shows a graph illustrating the relation between a cycle time(sec) of charge and discharge and a battery voltage (V) in an examplesystem manufactured in Experimental Example 4.

FIG. 6 shows a graph illustrating the relation between a charge time(sec) and a battery voltage (V) in a comparison system (I).

FIG. 7 shows a graph illustrating the relation between a cycle time(sec) of charge and discharge and a battery voltage (V) in a comparisonsystem (II).

DESCRIPTION OF EMBODIMENTS

Referring to FIGS. 1 to 3, battery systems including redox flowbatteries according to the first to third embodiments will behereinafter schematically described. In FIGS. 1 to 3, the same referencecharacters indicate components having the same names. Metal ions otherthan a vanadium ion shown in FIGS. 1 to 3 are merely illustrativeexamples. In FIGS. 1 to 3, a solid line arrow indicates charge, and abroken line arrow indicates discharge.

Redox flow batteries 100 according to the first to third embodimentshave similar basic structures, which will be described with reference toFIG. 1. Redox flow battery 100 is representatively connected to a powergeneration unit (for example, a solar photovoltaic power generator, awind power generator, or a common power plant) and to a load such as apower system or a consumer through a power conditioning system (PCS),charged by the power generation unit as a power supply source, anddischarged to provide power to the load. To be charged and discharged,the following battery system including redox flow battery 100 and acirculation mechanism (tanks, pipes, pumps) for circulating anelectrolyte through battery 100 is constructed.

Redox flow battery 100 includes a positive electrode cell 102 having apositive electrode 104 therein, a negative electrode cell 103 having anegative electrode 105 therein, and a membrane 101 separating cells 102and 103 from each other, through which ions permeate as appropriate.Positive electrode cell 102 is connected to a tank 106 for a positiveelectrode electrolyte through pipes 108, 110. Negative electrode cell103 is connected to a tank 107 for a negative electrode electrolytethrough pipes 109, 111. Pipes 108, 109 include pumps 112, 113 forcirculating the electrolytes of the electrodes, respectively. In redoxflow battery 100, the positive electrode electrolyte in tank 106 and thenegative electrode electrolyte in tank 107 are supplied to positiveelectrode cell 102 (positive electrode 104) and negative electrode cell103 (negative electrode 105) through circulation, respectively, throughpipes 108 to 111 and pumps 112, 113, to charge and discharge the batterythrough valence change reaction of the metal ion serving as activematerials in the electrolytes of both electrodes.

Redox flow battery 100 representatively has a form referred to as a cellstack, which includes a plurality of cells 102, 103 stacked therein.Cells 102, 103 are representatively structured with a cell frameincluding a bipolar plate (not shown) having positive electrode 104arranged on one surface and negative electrode 105 on the other surface,and a frame (not shown) having a liquid supply hole for supplying theelectrolytes and a liquid drainage hole for draining the electrolytes,and formed on the periphery of the bipolar plate. By stacking aplurality of cell frames, the liquid supply holes and the liquiddrainage holes form a fluid path for the electrolytes, which isconnected to pipes 108 to 111 as appropriate. The cell stack isstructured by successively and repeatedly stacking a set of the cellframe, positive electrode 104, membrane 101, negative electrode 105, andthe cell frame. A known structure may be used as appropriate as a basicstructure of the redox flow battery system.

In the redox flow battery according to the first embodiment, theabove-described positive electrode electrolyte and the above-describednegative electrode electrolyte each contain a vanadium ion, in which thepositive electrode electrolyte contains, in addition to a vanadium ion,a metal ion higher in redox potential than the vanadium ion (FIG. 1shows a manganese ion by way of example).

In the redox flow battery according to the second embodiment, theabove-described positive electrode electrolyte and the above-describednegative electrode electrolyte each contain a vanadium ion. The positiveelectrode electrolyte further contains, in addition to a vanadium ion, ametal ion higher in redox potential than the vanadium ion (FIG. 2 showsa manganese ion by way of example). The negative electrode electrolytefurther contains, in addition to a vanadium ion, a metal ion lower inredox potential than the vanadium ion (FIG. 2 shows a chromium ion byway of example).

In the redox flow battery according to the third embodiment, theabove-described positive electrode electrolyte and the above-describednegative electrode electrolyte each contain a vanadium ion. In additionto a vanadium ion, the negative electrode electrolyte further contains ametal ion lower in redox potential than the vanadium ion (FIG. 3 shows achromium ion by way of example).

A more specific explanation will be hereinafter made with reference toExperimental Examples. In each of Experimental Examples described below,the redox flow battery system shown in each of FIGS. 1 to 3 isstructured as a basic configuration, in which various types ofelectrolytes containing a vanadium ion were prepared in each of thepositive electrode and the negative electrode to perform charge anddischarge on various conditions.

Experimental Example 1

The following was prepared as an example system according to the firstembodiment.

(Electrolyte)

As a positive electrode electrolyte, 6 ml (6 cc) of an electrolytehaving a vanadium ion (tetravalent) concentration of 1.65 M and amanganese ion (divalent) concentration of 0.5M was prepared bydissolving sulfate salts (vanadium sulfate (tetravalent) and manganesesulfate (divalent)) in the sulfuric acid aqueous solution having asulfuric acid concentration (H₂SO₄aq) of 2.6M.

As a negative electrode electrolyte, 9 ml (9 cc) of an electrolytehaving a vanadium ion (trivalent) concentration of 1.7M was prepared bydissolving sulfate salt (vanadium sulfate (trivalent)) in the sulfuricacid aqueous solution (H₂SO₄aq) having a sulfuric acid concentration of1.75M. The amount of the negative electrode electrolyte is set to begreater than the amount of the positive electrode electrolyte, so thatthe battery reaction on the positive electrode side (including not onlyoxidation reaction of the vanadium ion but also oxidation reaction ofthe manganese ion) can be sufficiently caused during charge (which isthe same in Experimental Example 2 described later).

(Other Components)

A carbon felt was used for each of the positive and negative electrodes,and an ion exchange membrane was used for the membrane. The constituentmaterials of the electrode and the membrane can be selected asappropriate. The electrode made of carbon felt have advantages of (1)hardly generating oxygen gas and hydrogen gas on the positive electrodeside and the negative electrode side, respectively, (2) having arelatively large surface area, and (3) showing excellent circulation ofthe electrolyte. The ion exchange membranes have advantages of (1)attaining excellent isolation of the metal ions serving as activematerials of each electrode, and (2) having excellent permeability of anH⁺ ion (charge carrier inside a battery).

Then, in this Experimental Example 1, a small single cell batteryincluding an electrode having an area of 9 cm² was manufactured, and theprepared electrolyte for each of the above-described electrodes was usedto perform charge at a constant current of 630 mA (current density: 70mA/cm²). More specifically, the battery was charged until the state ofcharge (SOC) of a vanadium ion in the positive electrode electrolytereached 124%. The above-described state of charge shows the numericalvalue that is assumed to be set at 100 in the case where only a vanadiumion was used as active material. Thus, the state of charge exceeding100% means that the state of charge of the vanadium ion is approximately100% and Mn²⁺ is changed to Mn³⁺ (or tetravalent manganese) for charge.This charge was then switched to discharge, which was followed byrepetition of charge and discharge on the same charge conditions asthose described above. FIG. 4 shows the relation between the cycle timeof charge and discharge and the battery voltage.

The vanadium redox flow battery system was constructed as comparisonsystems. The basic configuration of each of the comparison systems isthe same as that of the above-described example system, and therefore,configured in the similar manner to the above-described example systemexcept that the electrolyte and the operating conditions were different.In this Experimental Example 1, as a positive electrode electrolyte anda negative electrode electrolyte, the vanadium electrolyte having avanadium ion (tetravalent) concentration of 1.7M in the positiveelectrode and a vanadium ion (trivalent) concentration of 1.7M in thenegative electrode was prepared by dissolving vanadium sulfate(tetravalent) in the sulfuric acid aqueous solution (H₂SO₄aq) having asulfuric acid concentration of 2.6M in the positive electrode anddissolving vanadium sulfate (trivalent) in the sulfuric acid aqueoussolution (H₂SO₄aq) having a sulfuric acid concentration of 1.75M in thenegative electrode.

Then, in the comparison system (I), a small single cell batteryincluding an electrode having an area of 9 cm² was manufactured. Then,the above-described vanadium electrolyte was used by 10 ml (10 cc) foreach of the positive electrode and the negative electrode, to performcharge at a constant current of 540 mA (current density: 60 mA/cm²).Furthermore, in the comparison system (I), even when the state of chargeof the vanadium ion in the positive electrode electrolyte exceeded thelevel equivalent to 100%, charge was continued for a while. FIG. 6 showsthe relation between the charge time and the battery voltage in thecomparison system (I).

On the other hand, the comparison system (II) is configured in thesimilar manner to the above-described comparison system (I) except thatthe amount of the electrolyte and the operating conditions aredifferent. Specifically, the above-described vanadium electrolyte wasused by 7 ml (7 cc) for each of the positive electrode and the negativeelectrode, to perform charge at a constant current of 630 mA (currentdensity: 70 mA/cm²). Then, in the comparison system (II), charge wasstopped and switched to discharge at the point of time when the voltagereached 1.6V (the state of charge of the vanadium ion: 78%). Then,charge and discharge were repeatedly performed in the similar manner.FIG. 7 shows the relation between the cycle time of charge and dischargeand the battery voltage in the comparison system (II).

Consequently, in the comparison system (I), the voltage rapidly rosefrom around 1.6V to 2.6V or higher, as shown in FIG. 6. When charge wasfurther continued, oxygen gas was generated from the positive electrodewhile hydrogen gas was generated from the negative electrode. Whendischarge was performed starting in such a state to further repeatcharge and discharge several times on the similar conditions (charge wascontinued until the state of charge exceeded 100%), there was a tendencythat the internal resistance of the battery was gradually increased andthe battery capacity was also decreased. When the cell was disassembledafter completion of the experiment, oxidation degradation of the carbonmaterial constituting the positive electrode was recognized.

On the other hand, in the comparison system (II), when the upper limitvoltage for charge was set at 1.6V, no generation of oxygen gas orhydrogen gas occurred. Furthermore, although charge and discharge wererepeated several times, neither the internal resistance of the batterywas increased nor the battery capacity was reduced. Thus, the operationcould be repeatedly performed with stability. However, in the comparisonsystem (II), the battery capacity that could be actually utilized is20.4 minutes with respect to the theoretical capacity of 30.4 minutes(the value converted into discharge time based on the vanadium ionconcentration of 1.7M, 7 ml, 630 mA) while the utilization rate of thevanadium ion is 67% (<90%).

On the other hand, in the example system, although the voltage risesfrom around 1.6V as shown in FIG. 4, this voltage rise is not so sharpbut relatively moderate as compared to the comparison system (I). It wasalso observed from the voltage characteristics after the voltage reached1.6 V or higher that, during charge, further oxidation reaction of thevanadium ion occurred in the positive electrode while oxidation reactionof the manganese ion (divalent) occurred. Furthermore, unlike thecomparison system (I), in the example system, even when charge wasperformed in the state where the state of charge of the positiveelectrode exceeded the level equivalent to 100%, a rise of the batteryvoltage was suppressed, and thus, at about 2V at most. In addition, inthe example system, it was confirmed that oxygen gas was not generatedand the electrode did not deteriorate when the cell was disassembledafter repetition of charge and discharge. Furthermore, the dischargetime (discharge capacity) of the example system was 23.7 minutes, whichwas 93.7% with respect to the theoretical capacity (25.3 minutes that isthe value converted into discharge time based on the vanadium ionconcentration of 1.65M, 6 ml, 630 mA), corresponding to the utilizationrate exceeding 90%. Furthermore, it was also confirmed that evenrepetition of charge and discharge did not cause a reduction in thebattery capacity and allowed a stable operation.

It can be said from the above-described Experimental Example 1 that whenat least the positive electrode electrolyte contains, in addition to avanadium ion, a metal ion higher in redox potential than the vanadiumion on the positive electrode side, the utilization rate of the vanadiumion can be effectively increased to improve the energy density.

Experimental Example 2

In Experimental Example 2, as a positive electrode electrolyte, 6 ml (6cc) of an electrolyte having a vanadium ion (tetravalent) concentrationof 1.65M and a manganese ion (divalent) concentration of 0.5M wasprepared by dissolving sulfate salts (vanadium sulfate (tetravalent) andmanganese sulfate (divalent)) in the sulfuric acid aqueous solution(H₂SO₄aq) having a sulfuric acid concentration of 2.6M. As a negativeelectrode electrolyte, 9 ml (9 cc) of an electrolyte having a vanadiumion (trivalent) concentration of 1.7M and a manganese ion (divalent)concentration of 0.5M was prepared by dissolving sulfate salts (vanadiumsulfate (trivalent) and manganese sulfate (divalent) in the sulfuricacid aqueous solution (H₂SO₄aq) having a sulfuric acid concentration of1.65M. Other configurations were similar to those of the example systemin Experimental Example 1.

Then, a small single cell battery (electrode area: 9 cm²) similar tothat of Experimental Example 1 was manufactured and the preparedelectrolyte of each of the positive electrode and negative electrode wasused to repeatedly perform charge and discharge on the conditionssimilar to those of the example system in Experimental Example 1. Inthis case, it was confirmed that the behavior of the voltagecharacteristics of the system in Experimental Example 2 was almost thesame as that of the example system in Experimental Example 1 while theutilization rate could also be set to exceed 90%. Furthermore, it wasconfirmed also in the system in Experimental Example 2 that oxygen gaswas not generated and the electrode did not deteriorate when the cellwas disassembled after repetition of charge and discharge.

Therefore, it can be said from Experimental Example 2 that theutilization rate of the vanadium ion can be effectively raised toimprove the energy density by the electrolyte in each of the positiveand negative electrodes containing, in addition to a vanadium ion, ametal ion higher in redox potential than the vanadium ion on thepositive electrode side.

Experimental Example 3

The following was prepared as an example system according to the secondembodiment.

As a positive electrode electrolyte, 6 ml (6 cc) of an electrolytehaving a vanadium ion (tetravalent) concentration of 1.65M, a manganeseion (divalent) concentration of 0.5M and a chromium ion (trivalent)concentration of 0.1M was prepared by dissolving sulfate salts (vanadiumsulfate (tetravalent), manganese sulfate (divalent) and chromium sulfate(trivalent)) in the sulfuric acid aqueous solution (H₂SO₄aq) having asulfuric acid concentration of 2.6M.

As a negative electrode electrolyte, 6 ml (6 cc) of an electrolytehaving a vanadium ion (trivalent) concentration of 1.65M, a manganeseion (divalent) concentration of 0.5M and a chromium ion (trivalent)concentration of 0.1M was prepared by dissolving sulfate salts (vanadiumsulfate (trivalent), manganese sulfate (divalent) and chromium sulfate(trivalent)) in the sulfuric acid aqueous solution (H₂SO₄aq) having asulfuric acid concentration of 1.75M.

A carbon felt was used for each of the positive and negative electrodes,and an ion exchange membrane was used for the membrane.

Then, in this Experimental Example 3, a small single cell batteryincluding an electrode having an area of 9 cm² was manufactured, and theabove-described prepared electrolyte of each of the electrodes was usedto perform charge at a constant current of 630 mA (current density: 70mA/cm²). More specifically, charge was performed until the state ofcharge (SOC) of the vanadium ion of the electrolyte in each electrodereached the level equivalent to 105%. The above-described state ofcharge shows a numerical value that is assumed to be set at 100 in thecase where only a vanadium ion is used as active material. The state ofcharge exceeding 100% means that, in addition to the fact that the stateof charge of the vanadium ion is approximately 100%, Mn²⁺ is changed toMn³⁺ (or tetravalent manganese) for charge in the positive electrodewhile Cr³⁺ is changed to Cr²⁺ for charge in the negative electrode. Thischarge was then switched to discharge, which was followed by repetitionof charge and discharge on the same charge conditions as those describedabove. The comparison system was configured as a comparison system (I)and a comparison system (II) in Experimental Example 1.

Consequently, in the example system according to the second embodiment,although the voltage rose from about 1.6V, this rise was not so sharpbut relatively moderate as compared to the comparison system (I). It wasalso observed from the voltage characteristics after the voltage reached1.6V or higher that, during charge, the positive electrode underwentfurther oxidation reaction of the vanadium ion and oxidation reaction ofthe manganese ion (divalent) while the negative electrode underwentfurther reduction reaction of the vanadium ion and reduction reaction ofthe chromium ion (trivalent). Furthermore, unlike the comparison system(I), in the example system of the second embodiment, even when chargewas performed in the state where the state of charge of each electrodeexceeded the level equivalent to 100%, a battery voltage rise wassuppressed, and thus, at about 2V at most. In addition, in the examplesystem according to the second embodiment, it was confirmed that oxygengas or hydrogen gas was not generated while the electrode did notdeteriorate when the cell was disassembled after repetition of chargeand discharge. Then, it was also confirmed that the discharge time(discharge capacity) of the example system according to the secondembodiment shows a utilization rate exceeding 90% with respect to thetheoretical capacity (25.3 minutes that is a value converted into thedischarge time based on the vanadium ion concentration of 1.65M, 6 ml,630 mA). Furthermore, it was also confirmed that even repetition ofcharge and discharge did not cause a reduction in the battery capacityand allowed a stable operation.

It can be said from the above-described Experimental Example 3 that whenat least the positive electrode electrolyte contains, in addition to avanadium ion, a metal ion higher in redox potential than the vanadiumion on the positive electrode side and when at least the negativeelectrode electrolyte contains, in addition to a vanadium ion, a metalion lower in redox potential than the vanadium ion on the negativeelectrode side, the utilization rate of the vanadium ion can beeffectively increased to improve the energy density. Furthermore, it canbe said that, in the above-described Experimental Example 3, the metalion species in the electrolyte of each of the positive and negativeelectrodes are partially the same, with the result that (1) a relativedecrease of the metal ions serving as active material hardly occurs,thereby allowing further suppression of occurrence of the side reaction;(2) variations in the liquid quantity resulting from liquid transfer canbe readily corrected; and (3) the manufacturability of the electrolyteis excellent.

Experimental Example 4

The following was prepared as an example system according to the thirdembodiment.

As a positive electrode electrolyte, 9 ml (9 cc) of an electrolytehaving a vanadium ion (tetravalent) concentration of 1.7M was preparedby dissolving sulfate salt (vanadium sulfate (tetravalent)) in thesulfuric acid aqueous solution (H₂SO₄aq) having a sulfuric acidconcentration of 2.6M.

As a negative electrode electrolyte, 6 ml (6 cc) of an electrolytehaving a vanadium ion (trivalent) concentration of 1.7M and a chromiumion (trivalent) concentration of 0.1M was prepared by dissolving sulfatesalts (vanadium sulfate (trivalent) and chromium sulfate (trivalent)) inthe sulfuric acid aqueous solution (H₂SO₄aq) having a sulfuric acidconcentration of 1.75M. The amount of the positive electrode electrolyteis set to be greater than the amount of the negative electrodeelectrolyte, so that the battery reaction on the negative electrode side(including not only reduction reaction of the vanadium ion but alsoreduction reaction of the chromium ion) can be sufficiently causedduring charge (which is the same in Experimental Example 5 describedlater).

A carbon felt was used for each of the positive and negative electrodes,and an ion exchange membrane was used for the membrane.

Then, in this Experimental Example 4, a small single cell batteryincluding an electrode having an area of 9 cm² was manufactured and theabove-described prepared electrolyte in each of the electrodes was usedto perform charge at a constant current of 630 mA (current density: 70mA/cm²). More specifically, charge was performed until the state ofcharge (SOC) of the vanadium ion in the negative electrode electrolytereached the level equivalent to 109%. The above-described state ofcharge shows a numerical value that is assumed to be set at 100 in thecase where only a vanadium ion was used as active material. Thus, thestate of charge exceeding 100% means that the state of charge of thevanadium ion is approximately 100% and Cr³⁺ is changed to Cr²⁺ forcharge. This charge was then switched to discharge, which was followedby repetition of charge and discharge on the same charge conditions asthose described above. FIG. 5 shows the relation between the cycle timeof charge and discharge and the battery voltage. The comparison systemwas configured as a comparison system (I) and a comparison system (II)of Experimental Example 1.

Consequently, in the example system according to the third embodiment,although the voltage rose from about 1.6V as shown in FIG. 5, this risewas not so sharp but relatively moderate as compared to the comparisonsystem (I). It was also observed from the voltage characteristics afterthe voltage reached 1.6V or higher that, during charge, the negativeelectrode underwent further reduction reaction of the vanadium ion andreduction reaction of the chromium ion (trivalent). Furthermore, unlikethe comparison system (I), in the example system according to the thirdembodiment, even when the charge was performed in the state where thestate of charge of the negative electrode exceeded the level equivalentto 100%, a battery voltage rise was suppressed, and thus, at about 2V atmost. In addition, no generation of hydrogen gas was observed in theexample system according to the third embodiment. Then, the dischargetime (discharge capacity) of the example system according to the thirdembodiment was 25.9 minutes corresponding to 99.6% with respect to thetheoretical capacity (26 minutes which is a value converted into thedischarge time based on the vanadium ion concentration of 1.75M, 6 ml,630 mA). Thus, the capacity of nearly 100% was achieved and theutilization rate exceeding 90% was also achieved. Furthermore, it wasalso confirmed that even repetition of charge and discharge did notcause a reduction in the battery capacity and allowed a stableoperation.

It can be said from the above-described Experimental Example 4 that theutilization rate of the vanadium ion can be effectively increased toimprove the energy density by at least the negative electrodeelectrolyte containing, in addition to a vanadium ion, a metal ion lowerin redox potential than the vanadium ion on the negative electrode side.

Experimental Example 5

In Experimental Example 5, the electrolyte containing a vanadium ion anda chromium ion was used as an electrolyte for each of the positiveelectrode and the negative electrode. Specifically, as a positiveelectrode electrolyte, sulfate salt (chromium sulfate (trivalent)) wasfurther used in addition to the same materials as those in the examplesystem of Experimental Example 4 to prepare 9 ml (9 cc) of anelectrolyte having a vanadium ion (tetravalent) concentration of 1.7Mand a chromium ion (trivalent) concentration of 0.1M. A negativeelectrode electrolyte similar to that in the example system ofExperimental Example 4 was prepared (a vanadium ion (trivalent)concentration of 1.7M and a chromium ion (trivalent) concentration of0.1M, 6 ml (6 cc)). Other configurations were the same as those in theexample system of Experimental Example 4.

Then, a small single cell battery similar to that in ExperimentalExample 4 (an electrode area: 9 cm²) was manufactured and theelectrolyte in each of the prepared positive and negative electrodes wasused, to perform charge until the state of charge of the vanadium ionreached the level equivalent to 110% at a constant current of 630 mA(current density: 70 mA/cm²) in the similar manner to ExperimentalExample 4. Then, the behavior of the voltage characteristics of thesystem in Experimental Example 5 showed almost the same behavior as thatof the example system in Experimental Example 4. Furthermore, thedischarge time of the system in Experimental Example 5 was 25 minutes,which was 98% with respect to the theoretical capacity (26 minutes).Thus, it was confirmed that the battery capacity of nearly 100% wasachieved and the utilization rate exceeding 90% could also be achieved.Furthermore, also in the system of Experimental Example 5, repetition ofcharge and discharge still allowed a stable operation and did not causegeneration of hydrogen gas.

It can be said from Experimental Example 5 that the utilization rate ofthe vanadium ion can be effectively increased to improve the energydensity also when the electrolyte in each of the positive and negativeelectrodes contains, in addition to a vanadium ion, a metal ion lower inredox potential than the vanadium ion on the negative electrode side.

The present invention is not limited to the above-described embodimentsbut can be modified as appropriate without deviation from the contentsof the present invention. For example, the type and the concentration ofthe metal ion, the concentration of the solvent of the electrolyte, andthe like can be changed as appropriate.

INDUSTRIAL APPLICABILITY

The redox flow battery according to the present invention can besuitably used as a large-capacity storage battery for stabilizingvariations in power generation output, storing surplus generated power,and load leveling for power generation of new energy such as solarphotovoltaic power generation and wind power generation. The redox flowbattery according to the present invention can also be suitably used asa large-capacity storage battery attached to a common power plant forvoltage sag and power failure prevention and for load leveling.

REFERENCE SIGNS LIST

100 redox flow battery, 101 membrane, 102 positive electrode cell, 103negative electrode cell, 104 positive electrode, 105 negative electrode,106 tank for positive electrode electrolyte, 107 tank for negativeelectrode electrolyte, 108, 109, 110, 111 pipe, 112, 113 pump.

1. A redox flow battery performing charge and discharge by supplying apositive electrode electrolyte and a negative electrode electrolyte to abattery cell, each of said positive electrode electrolyte and saidnegative electrode electrolyte containing a vanadium ion, and at leastone of said positive electrode electrolyte and said negative electrodeelectrolyte further containing at least one of a metal ion higher inredox potential than the vanadium ion and a metal ion lower in redoxpotential than the vanadium ion.
 2. The redox flow battery according toclaim 1, wherein at least said positive electrode electrolyte furthercontains a metal ion higher in redox potential than the vanadium ion. 3.The redox flow battery according to claim 1, wherein each of saidpositive electrode electrolyte and said negative electrode electrolytefurther contains a metal ion higher in redox potential than the vanadiumion.
 4. The redox flow battery according to claim 1, wherein said metalion higher in redox potential is at least one type of metal ionsselected from a manganese ion, a lead ion, a cerium ion, and a cobaltion, and a total concentration of said metal ion higher in redoxpotential in an electrolyte containing said metal ion higher in redoxpotential is not less than 0.1M and not more than 5M.
 5. The redox flowbattery according to claim 1, wherein said metal ion higher in redoxpotential is at least one type of manganese ions of a divalent manganeseion and a trivalent manganese ion.
 6. The redox flow battery accordingto claim 1, wherein the electrolyte containing said metal ion higher inredox potential contains at least one type of manganese ions of adivalent manganese ion and a trivalent manganese ion, and tetravalentmanganese.
 7. The redox flow battery according to claim 1, wherein atleast said positive electrode electrolyte further contains a metal ionhigher in redox potential than the vanadium ion, and at least saidnegative electrode electrolyte further contains a metal ion lower inredox potential than the vanadium ion.
 8. The redox flow batteryaccording to claim 1, wherein at least one of said positive electrodeelectrolyte and said negative electrode electrolyte further containseach of the metal ion higher in redox potential than the vanadium ionand the metal ion lower in redox potential than the vanadium ion.
 9. Theredox flow battery according to claim 1, wherein said metal ion higherin redox potential is at least one type of metal ions selected from amanganese ion, a lead ion, a cerium ion, and a cobalt ion, said metalion lower in redox potential is at least one type of metal ions of achromium ion and a zinc ion, and each of a total concentration of themetal ions higher in redox potential in an electrolyte containing saidmetal ions higher in redox potential and a total concentration of themetal ions lower in redox potential in an electrolyte containing saidmetal ions lower in redox potential is not less than 0.1M and not morethan 5M.
 10. The redox flow battery according to claim 1, wherein saidmetal ion higher in redox potential is at least one type of manganeseions of a divalent manganese ion and a trivalent manganese ion, and saidmetal ion lower in redox potential is at least one type of chromium ionsof a divalent chromium ion and a trivalent chromium ion.
 11. The redoxflow battery according to claim 1, wherein the electrolyte containingsaid metal ion higher in redox potential contains at least one type ofmanganese ions of a divalent manganese ion and a trivalent manganeseion, and tetravalent manganese, and said metal ion lower in redoxpotential is at least one type of chromium ions of a divalent chromiumion and a trivalent chromium ion.
 12. The redox flow battery accordingto claim 1, wherein at least said negative electrode electrolyte furthercontains a metal ion lower in redox potential than the vanadium ion. 13.The redox flow battery according to claim 1, wherein each of saidpositive electrode electrolyte and said negative electrode electrolytefurther contains a metal ion lower in redox potential than the vanadiumion.
 14. The redox flow battery according to claim 1, wherein said metalion lower in redox potential is at least one type of metal ions of achromium ion and a zinc ion, and a total concentration of the metal ionslower in redox potential in an electrolyte containing said metal ionslower in redox potential is not less than 0.1M and not more than 5M. 15.The redox flow battery according to claim 1, wherein said metal ionlower in redox potential is at least one type of chromium ions of adivalent chromium ion and a trivalent chromium ion.
 16. The redox flowbattery according to claim 1, wherein each of said positive electrodeelectrolyte and said negative electrode electrolyte contains a sulfateanion.
 17. The redox flow battery according to claim 1, wherein asolvent of each of said positive electrode electrolyte and said negativeelectrode electrolyte is an H₂SO₄ aqueous solution, and a sulfuric acidconcentration of each of said positive electrode electrolyte and saidnegative electrode electrolyte is not more than 5M.
 18. The redox flowbattery according to claim 1, wherein an operation is performed suchthat a state of charge of an electrolyte of an electrode containing atleast one of said metal ion higher in redox potential and said metal ionlower in redox potential exceeds 90%.